Process for preparing self-binding pigment particle suspensions

ABSTRACT

The invention relates to a process for preparing self-binding pigment particle suspensions, to a self-binding pigment particle suspension as well as to a paper product comprising self-binding pigment particles and to the use of the self-binding pigment particle suspension as filler material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/238,508, filed Apr. 21, 2014, now U.S. Pat. No. 9,670,366, which isthe U.S. national phase of PCT Application No. PCT/EP2012/066302, filedAug. 22, 2012, which claims priority to European Application No.11179604.1, filed Aug. 31, 2011 and U.S. Provisional Application No.61/531,662, filed Sep. 7, 2011, the content of which is herebyincorporated by reference.

BACKGROUND OF THE INVENTION

The invention relates to a process for preparing self-binding pigmentparticle suspensions, to a self-binding pigment particle suspension aswell as to a paper product comprising self-binding pigment particles andto the use of the self-binding pigment particle suspension as fillermaterial.

Mineral materials and binders are among the main constituents used inthe manufacture of numerous products such as paints, paper and plasticmaterials. Therein, mineral materials such as calcium carbonate andother particulate materials contribute mechanical and opticalproperties, while the binder, generally latex-based and in the form ofaqueous suspensions or dispersions, provide the necessary adhesion andcohesion for the respective constituents of the end product to beproduced.

In order to avoid the logistic difficulties of handling mineralmaterials and binders separately, and further to avoid the unwantedphysical and chemical interactions developed in comparable mixtures ofmineral materials and binders, self-binding pigment particles have beendeveloped and are known to industry. In this regard, self-bindingpigment particles contributing both the properties of the mineralmaterial and of the binder may be directly implemented in a variety ofapplications.

This unique product named self-binding pigment particles refers todistinct, solid particles, formed of mineral material and binder thatare intimately bound to one another. The internal cohesion forces aresuch as to provide the self-binding pigment particles with excellentmechanical stability.

Self-binding pigment particles are prepared by a process implementing atleast one step of grinding mineral materials in the presence of binder,where grinding refers to an operation leading to a reduction in theparticle size; the mineral materials in the self-binding pigmentparticles have a smaller diameter than the initial mineral material usedto produce them. Such self-binding pigment particles are described in anumber of documents, including WO 2006/008657, WO 2006/128814, and WO2008/139292.

However, there is still a need in the art for a process for preparingself-binding pigment particle suspensions which would solve one or moreof the following multifaceted technical problems:

-   -   to prepare a suspension of self-binding pigment particles        resulting in a paper coating having a content of binder that is        below the content of latex binder typically used in the        preparation of such paper coatings;    -   to prepare a suspension of self-binding pigment particles        allowing for the provision of a filler material for paper        products such that the paper product has a sufficient tensile        index, preferably a tensile index of at least 10 Nm/g;    -   to prepare a suspension of self-binding pigment particles such        that the content of components based on fossil resources in the        obtained suspension is reduced, that is to say the self-binding        pigment particle suspension comprises a binder that is obtained        from renewable resources;    -   to prepare a suspension of self-binding pigment particles such        that the obtained suspension provides a higher biodegradability        than a corresponding suspension prepared with latex-based binder        typically used in the preparation of such a suspension;    -   to prepare a suspension of self-binding pigment particles having        a sufficient microbiological stability such that a fouling of        the obtained suspension and end products prepared from such a        suspension is delayed;    -   to prepare a suspension of self-binding pigment particles        containing less sticky materials such that less deposits are        observed on the equipment used during preparation, storage and        application of the suspension, that is to say a suspension that        provides a better handling.

There is a continuous need for improving processes for the preparationof self-binding pigment particle suspensions which addresses theforegoing technical problems described and especially allows forreducing the content of polymeric latex-based binder in suchsuspensions.

SUMMARY OF THE INVENTION

Accordingly, it is an objective of the present invention to provide aprocess for preparing self-binding pigment particle suspensions having areduced content of latex-based binder. A further objective is to providea process for preparing self-binding pigment particle suspensions suchthat a paper product prepared from such a suspension features a tensileindex of at least 10 Nm/g. Even a further objective is to provide aprocess for preparing self-binding pigment particle suspensions having areduced content of components based on fossil resources. A still furtherobjective is to provide a process for preparing self-binding pigmentparticle suspensions having an increased biodegradability compared to asuspension prepared with a latex binder. Another objective of thepresent invention is to provide a process for preparing self-bindingpigment particle suspensions providing a sufficient microbiologicalstability. A further objective is to provide a process for preparingself-binding pigment particle suspensions that can be carried out undercost-efficient conditions, i.e. by avoiding cost-intensive raw materialsand/or intensive cleaning steps. Further objectives can be gathered fromthe following description of the invention.

While the Applicant knows as a solution the unpublished European PatentApplication Number 11 160900.4 describing a process for preparing ofself-binding pigment particles comprising the steps of: a) providing anaqueous mineral pigment suspension, b) providing at least one polymericbinder, wherein the binder comprises at least one carboxymethylcellulosehaving a degree of carboxylation in the range of 0.4 to 2.0 and havingan intrinsic viscosity in the range of 3 to 300 ml/g, c) mixing thebinder of step b) with the aqueous mineral pigment material suspensionof step a) and adjusting the solids content of the obtained suspensionso that it is from 45 to 80 wt.-%, based on the total weight of thesuspension, and d) grinding the aqueous mineral material suspension ofstep c), and the unpublished European Patent Application Number 11160926.9 describing a process for preparing of self-binding pigmentparticles comprising the steps of: a) providing an aqueous mineralpigment suspension, b) providing at least one polymeric binder, whereinthe binder comprises at least one modified polysaccharide having adegree of carboxylation in the range of 0.4 to 2.0 and having anintrinsic viscosity in the range of 3 to 300 ml/g, wherein the carbon ofthe binder shows a rate of nuclear transformation of ¹⁴C to ¹²C ofbetween 900 and 920 transformations per hour and per gram carbon in thebinder; c) mixing the binder of step b) with the aqueous mineral pigmentmaterial suspension of step a) and adjusting the solids content of theobtained suspension so that it is from 45 to 80 wt.-%, based on thetotal weight of the suspension, and d) grinding the aqueous mineralmaterial suspension of step c) until the fraction of self-bindingpigment particles having a particle size of less than 1 μm is greaterthan 5 wt.-%, based on the total weight of the pigment particles, theforegoing and other objects are solved by the subject-matter as definedherein in the present invention.

According to a first aspect of the present invention, a process forpreparing self-binding pigment particle suspensions is provided, whereinthe process comprises the steps of:

a) providing an aqueous pigment material suspension,

b) providing at least one polymeric binder, wherein the binder comprisesat least one polysaccharide comprising galactose and/or mannose units,

c) mixing the polymeric binder of step b) with the aqueous pigmentmaterial suspension of step a); and

d) grinding the aqueous pigment material suspension of step c).

The inventors surprisingly found that the foregoing process according tothe present invention leads to self-binding pigment particle suspensionsproviding a reduced content of binder as well as of sticky materials andof components based on fossil resources, a sufficient biodegradabilityand microbial stability and imparts a tensile index of at least 10 Nm/gto paper products prepared from such a suspension. More precisely, theinventors found that the properties of a suspension of self-bindingpigment particles can be improved by the addition of a definedpolysaccharide comprising galactose and/or mannose units as the binder.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1: illustrates the effect of the self-binding pigment particlesuspensions on the tensile index for handsheets prepared from suchsuspensions.

FIG. 2: illustrates the effect of the self-binding pigment particlesuspensions on the internal bond (in z-Direction) for handsheetsprepared from such suspensions.

FIG. 3: illustrates the maximum force, F_(max), required to make thefirst crack into a tablet.

DETAILED DESCRIPTION OF THE INVENTION

It should be understood that for the purposes of the present invention,the following terms have the following meaning:

The term aqueous “pigment material” suspension in the meaning of thepresent invention encompasses natural and/or synthetic materials, likecalcium carbonate, talc, chalk, dolomite, mica, titanium dioxide, etc.

The term aqueous pigment material “suspension” in the meaning of thepresent invention comprises insoluble solids and water and optionallyfurther additives and usually contains large amounts of solids and,thus, is more viscous and generally of higher density than the liquidfrom which it is formed.

The term “binder” as used in the present invention is a compound that isconventionally used to bind together two or more other materials inmixtures. However, in the process of the present invention the binderhas an effect other than aggregation, namely the effect of improving thetensile index of products prepared from self-binding pigment particlesuspensions.

The term “polysaccharide comprising galactose and/or mannose units” inthe meaning of the present invention refers to polymeric carbohydratestructures, formed by a plurality of galactose and/or mannose unitsjoined together by glycosidic bonds. These structures are often linear,but may contain various degrees of branching.

Another aspect of the present invention is directed to a self-bindingpigment particle suspension obtainable by the process.

A further aspect of the present invention is directed to a paper productcomprising self-binding pigment particles, wherein the pigment particlesare at least partially coated with at least one polysaccharidecomprising galactose and/or mannose units. It is preferred that thepaper product has a tensile index of at least 10 Nm/g, preferably atleast 15 Nm/g, more preferably at least 20 Nm/g and most preferably atleast 22 Nm/g at a filler loading of 20 wt.-%.

A still further aspect of the present invention is directed to the useof the self-binding pigment particle suspension as filler material. Itis preferred that the filler material is used in paper, plastics, paint,concrete and/or agriculture applications. It is further preferred thatthe self-binding pigment particle suspension is used in wet end processof a paper machine, in cigarette paper and/or coating applications, oras a support for rotogravure and/or offset and/or digital printing. Itis also preferred that the self-binding pigment particle suspension isused to reduce sun light and UV exposure of plant leaves.

When in the following reference is made to preferred embodiments ortechnical details of the inventive process for preparing self-bindingpigment particle suspensions, it is to be understood that thesepreferred embodiments and technical details also refer to the inventiveself-binding pigment particle suspension, the inventive paper productcomprising a pigment material as well as to the use of the self-bindingpigment particle suspension defined herein and vice versa (as far asapplicable). If, for example, it is set out that the aqueous pigmentmaterial suspension provided in the process for preparing self-bindingpigment particle suspensions comprises a pigment material selected fromthe group comprising calcium carbonate, calcium carbonate containingminerals, mixed carbonate based fillers, or mixtures thereof, also theinventive self-binding pigment particle suspension, the inventive paperproduct comprising a pigment material as well as the use of theself-binding pigment particle suspension preferably comprise a pigmentmaterial selected from the group comprising calcium carbonate, calciumcarbonate containing minerals, mixed carbonate based fillers, ormixtures thereof.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the pigmentmaterial suspension of step a) comprises a pigment material selectedfrom the group comprising calcium carbonate, calcium carbonatecontaining minerals, mixed carbonate based fillers, or mixtures thereof,and wherein the calcium carbonate containing minerals preferablycomprise dolomite, and the mixed carbonate based fillers are preferablyselected from calcium associated with magnesium, clay, talc,talc-calcium carbonate mixtures, calcium carbonate-kaolin mixtures, ormixtures of natural calcium carbonate with aluminium hydroxide, mica orwith synthetic or natural fibers or co-structures of minerals,preferably talc-calcium carbonate or talc-titanium dioxide or calciumcarbonate-titanium dioxide co-structures.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the calciumcarbonate is a ground natural calcium carbonate, a precipitated calciumcarbonate, a modified calcium carbonate, or a mixture thereof.

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, the binder ofstep b) comprises at least one polysaccharide comprising galactose andmannose units.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the binder of stepb) comprises a cationic derivative of the at least one polysaccharide.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the binder of stepb) comprises at least one polysaccharide comprising a linear chain of1,4-linked β-D-mannopyranosyl units, preferably the linear chain of1,4-linked β-D-mannopyranosyl units is 1,6-linked withα-D-galactopyranosyl units.

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, the binder ofstep b) comprises at least one polysaccharide having a ratio of mannoseunits to galactose units from 6:1 to 1:1, preferably from 5:1 to 1:1,more preferably from 4:1 to 1:1 and most preferably from 3:1 to 1:1.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the binder of stepb) is in form of a hydrocolloidal solution or a dry material, preferablyin form of a hydrocolloidal solution.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the binder of stepb) is in form of a hydrocolloidal solution having a binder concentrationfrom 0.05 wt.-% to 10 wt.-%, preferably from 0.1 wt.-% to 5 wt.-%, morepreferably from 0.1 wt.-% to 2 wt.-% and most preferably from 0.1 wt.-%to 1 wt.-%, based on the total weight of the solution.

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, the binder instep c) is added to the aqueous pigment material suspension in an amountfrom 0.1 wt.-% and 10 wt.-%, preferably from 0.05 wt.-% to 5.0 wt.-%,more preferably from 0.1 wt.-% to 2 wt.-% and most preferably from 0.25wt.-% to 1 wt.-%, based on the total weight of the pigment materialsuspension.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the solids contentin step c) is adjusted such that it is at least 1 wt.-%, preferably from1 wt.-% to 80 wt.-%, more preferably from 5 wt.-% to 60 wt.-%, even morepreferably from 10 wt.-% to 50 wt.-% and most preferably from 15 wt.-%to 45 wt.-%, based on the total weight of the pigment materialsuspension.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, grinding step d) iscarried out during and/or after step c), preferably after step c).

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, grinding stepd) is carried out at a temperature from 10° C. to 110° C., preferablyfrom 20° C. to 60° C. and most preferably from 20° C. to 45° C.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, grinding step d) iscarried out until the fraction of self-binding pigment particles havinga particle size of less than 1 μm is greater than 5 wt.-%, preferablygreater than 20 wt.-%, more preferably greater than 40 wt.-%, morepreferably greater than 50 wt.-%, and most preferably greater than 60wt.-%, based on the total weight of the pigment particles.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, grinding step d) iscarried out in batch or continuously, preferably continuously.

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, the processfurther comprises step e) of concentrating the obtained pigment materialsuspension such that the solids content in the suspension is at least 45wt.-%, preferably from 45 wt.-% to 80 wt.-%, more preferably from 50wt.-% to 80 wt.-%, even more preferably, from 60 wt.-% to 79 wt.-% andmost preferably from 65 wt.-% to 78 wt.-%, based on the total weight ofthe pigment material suspension.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, concentration stepe) is carried out before or after step d)

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, before or during orafter step c) and/or step d) a dispersing agent is added.

As set out above, the inventive process for preparing self-bindingpigment particle suspensions comprises the steps a), b), c) and d). Inthe following, it is referred to further details of the presentinvention and especially the foregoing steps of the inventive processfor preparing self-binding pigment particle suspensions.

Step a): Provision of an Aqueous Pigment Material Suspension

According to step a) of the process of the present invention, an aqueouspigment material suspension is provided.

The aqueous pigment material suspension is obtained by mixing aparticulate pigment material with water. The pigment material to beprocessed according to the inventive process may be selected fromcalcium carbonate, calcium carbonate containing minerals, mixedcarbonate based fillers, or mixtures thereof.

According to a preferred embodiment of the present invention, thepigment material is a calcium carbonate. Calcium carbonate may be aground natural calcium carbonate, also named heavy calcium carbonate, aprecipitated calcium carbonate, also named light calcium carbonate, amodified calcium carbonate or a mixture thereof.

“Ground natural calcium carbonate” (GNCC) in the meaning of the presentinvention is a calcium carbonate obtained from natural sources, such aslimestone, marble, chalk and mixtures thereof, and processed through awet and/or dry treatment such as grinding, screening and/orfractionating, for example by a cyclone or classifier.

“Modified calcium carbonate” (MCC) in the meaning of the presentinvention may feature a natural ground or precipitated calcium carbonatewith an internal structure modification or a surface-reaction product.According to a preferred embodiment of the present invention, themodified calcium carbonate is a surface-reacted calcium carbonate.

“Precipitated calcium carbonate” (PCC) in the meaning of the presentinvention is a synthesized material, generally obtained by precipitationfollowing the reaction of carbon dioxide and lime in an aqueousenvironment or by precipitation of a calcium and carbonate source inwater or by precipitation of calcium and carbonate ions, for exampleCaCl₂ and Na₂CO₃, out of solution. Precipitated calcium carbonate existsin three primary crystalline forms: calcite, aragonite and vaterite, andthere are many different polymorphs (crystal habits) for each of thesecrystalline forms. Calcite has a trigonal structure with typical crystalhabits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonalprismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC).Aragonite is an orthorhombic structure with typical crystal habits oftwinned hexagonal prismatic crystals, as well as diverse assortment ofthin elongated prismatic, curved bladed, steep pyramidal, chisel shapedcrystals, branching tree, and coral or worm-like form.

In one preferred embodiment of the inventive process, the pigmentmaterial comprises a mixture of ground natural calcium carbonate, aprecipitated calcium carbonate or a modified calcium carbonate. Forexample, if the pigment material comprises a mixture of ground naturalcalcium carbonate, the pigment material comprises a mixture of at leasttwo pigment materials selected from limestone, marble and chalk.

According to one embodiment of the present invention, the calciumcarbonate-containing mineral comprises dolomite.

According to a preferred embodiment, the mixed carbonate based fillersare selected from calcium associated with magnesium and analogues orderivatives, various matter such as clay or talc or analogues orderivatives, and mixtures of these fillers, such as, for example,talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixturesof natural calcium carbonate with aluminium hydroxide, mica or withsynthetic or natural fibers or co-structures of minerals such astalc-calcium carbonate or talc-titanium dioxide or calciumcarbonate-titanium dioxide co-structures.

The particulate pigment material of the aqueous pigment materialsuspension provided in step a) may have a particle size distribution asconventionally employed for the material(s) involved in the type ofproduct to be produced. In general, it is preferred that the pigmentmaterial particles in the suspension have a weight median particlediameter d₅₀ value of from 0.05 μm to 100 μm, preferably from 0.1 μm to60 μm and more preferably from 0.4 μm to 20 μm, most preferably from 0.6μm to 10 μm, for example from 0.7 μm to 1.0 as measured using aSedigraph™ 5120 of Micromeritics Instrument Corporation.

The value d_(x) represents the diameter relative to which x % by weightof the particles have diameters less than d_(x). This means that the d₂₀value is the particle size at which 20 wt.-% of all particles aresmaller, and the d₇₅ value is the particle size at which 75 wt.-% of allparticles are smaller. The d₅₀ value is thus the weight median particlesize at which 50 wt.-% of all grains are bigger or smaller than thisparticle size. The method and the instrument are known to the skilledperson and are commonly used to determine grain size of fillers andpigments. The measurement is carried out in an aqueous solution of 0.1wt.-% Na₄P₂O₇. The samples are dispersed using a high speed stirrer andsupersonics.

In a preferred embodiment, the pigment material particles in thesuspension exhibit a BET specific surface area of from 0.1 m²/g to 200m²/g, more preferably 3 m²/g to 25 m²/g, most preferably 5 m²/g to 15m²/g and even more preferably 6 m²/g to 12 m²/g, measured using nitrogenand the BET method according to ISO 9277.

The pigment material particles of the present invention are suspended inwater and thus form an aqueous suspension or slurry of pigment material.

Preferably, the aqueous pigment material suspension provided in step a)has a solids content from 1 wt.-% to 80 wt.-%, preferably from 5 wt.-%to 60 wt.-%, more preferably from 10 wt.-% to 50 wt.-% and mostpreferably from 15 wt.-% to 45 wt.-%, based on the total weight of thepigment material suspension.

Step b): Provision of at Least One Polymeric Binder

According to step b) of the process of the present invention, at leastone polymeric binder is provided. Said polymeric binder comprises atleast one polysaccharide comprising galactose and/or mannose units.

In case all the monosaccharide units in the at least one polysaccharideare of the same type, the polysaccharide is also named ahomopolysaccharide or homoglycan. If the at least one polysaccharide iscomposed of more than one type of monosaccharide units, thepolysaccharide is also named a heteropolysaccharide or heteroglycan.

In one preferred embodiment of the present invention, the at least onepolysaccharide is a homopolysaccharide. Preferably, thehomopolysaccharide is composed of a plurality of repeating units ofgalactose. More preferably, the repeating units of galactose areα-D-galactopyranosyl units and/or β-D-galactopyranosyl units. In onepreferred embodiment, the homopolysaccharide is composed of repeatingunits of β-D-galactopyranose or α-D-galactopyranose. In an especiallypreferred embodiment, the homopolysaccharide is a linear chain of1,4-linked β-D-galactopyranosyl units.

Additionally or alternatively, the homopolysaccharide is composed of aplurality of repeating units of mannose. More preferably, the repeatingunits of mannose are α-D-mannopyranosyl units and/or β-D-mannopyranosylunits. In one preferred embodiment, the homopolysaccharide is composedof repeating units of β-D-mannopyranose or α-D-mannopyranose. In anespecially preferred embodiment, the homopolysaccharide is a linearchain of 1,4-linked β-D-mannopyranosyl units.

In another preferred embodiment of the present invention, the at leastone polysaccharide is a heteropolysaccharide comprising mannose unitsand galactose units. Preferably, the heteropolysaccharide comprisesgalactose units selected from α-D-galactopyranose, β-D-galactopyranoseand mixtures thereof and mannose units selected from α-D-mannopyranose,β-D-mannopyranose and mixtures thereof.

For example, the heteropolysaccharide comprises β-D-mannopyranosyl unitsand α-D-galactopyranosyl units. In one preferred embodiment, theheteropolysaccharide comprises a linear chain of 1,4-linkedβ-D-mannopyranosyl units to which α-D-galactopyranosyl units are1,6-linked. Preferably, the heteropolysaccharide comprises a linearchain of 1,4-linked β-D-mannopyranosyl units to which singleα-D-galactopyranosyl units are 1,6-linked.

If the at least one polysaccharide comprises a heteropolysaccharidecomprising mannose units and galactose units, the at least onepolysaccharide has a ratio of mannose units to galactose units from 6:1to 1:1, preferably from 5:1 to 1:1, more preferably from 4:1 to 1:1 andmost preferably from 3:1 to 1:1, e.g. in a ratio of mannose units togalactose units of 2:1.

For example, the at least one polysaccharide comprises a linear chain of1,4-linked β-D-mannopyranosyl units with 1,6-linked α-D-galactopyranosylunits on average to every second mannose unit.

Additionally or alternatively, a derivative of the at least onepolysaccharide may be utilized in the process of the present invention.Such derivative may be obtained, for example, by modifying thepolysaccharide through the use of enzymes, acids, oxidation media,temperature, radiation etc. Methods for preparing such derivatives areknown to the skilled person. For example, a modification may be obtainedby etherification of the polysaccharide with propyleneoxide orethyleneoxide resulting in a hydroxypropyl derivative or hydroxyethylderivative.

In one preferred embodiment of the present invention, the bindercomprises an anionic derivative of the at least one polysaccharide. Forexample, the anionic derivative of the at least one polysaccharide is acarboxymethyl derivative and/or carboxymethyl hydroxypropyl derivativeand/or carboxymethyl hydroxyethyl derivative of the at least onepolysaccharide.

In another preferred embodiment of the present invention, the bindercomprises a cationic derivative of the at least one polysaccharide. Forexample, the cationic derivative of the at least one polysaccharide isobtained by reacting the polysaccharide with derivatives of quaternaryammonium salts.

Methods for preparing such anionic and/or cationic derivatives of the atleast one polysaccharide are known to the skilled person.

The cationic derivative and/or anionic derivative of the at least onepolysaccharide preferably has a degree of substitution of the hydroxylgroups of at least 0.01, more preferably of at least 0.05 and may be ashigh as 1.0. A suitable degree of substitution of the hydroxyl groupsmay be from 0.1 to 0.5.

The molecular weight of the at least one polysaccharide preferablyranges from 1 000 to 1 000 000 Da and is generally about 220 000 Da. Themolecular weight of the at least one polysaccharide can be adjusted bythe treatment with hydrogen peroxide (H₂O₂).

In one preferred embodiment of the present invention, the at least onepolysaccharide is guar and/or a guar derivative. Guar comprises anatural heteropolysaccharide (guaran) consisting of galactose units andmannose units usually in the ratio of 1:2 and is the endosperm componentof guar seeds. In general, guar comprises a linear chain of 1,4-linkedβ-D-mannopyranosyl units with 1,6-linked α-D-galactopyranosyl units.Guar seeds containing about 14 to 17 wt.-% husk, 35 to 42 wt.-%endosperm and 43 to 47 wt.-% embryo, are usually dry-milled and screenedto separate out the endosperm which is the industrial guar of commerce.

In one preferred embodiment, guar is used in its natural form in theprocess of the present invention, i.e. the heteropolysaccharide isuntreated.

Additionally or alternatively, a guar derivative may be utilized in theprocess of the present invention. A guar derivative is obtained, forexample, by modifying the heteropolysaccharide through the use ofenzymes, acids, oxidation media, temperature, radiation etc. Methods forpreparing such guar derivatives are known to the skilled person. Forexample, a modification may be obtained by the use of a commerciallyavailable α-D-galactosidase enzyme which is useful to removeα-D-galactopyranosyl units. By controlling the length of time that theguaran is exposed to the α-D-galactosidase enzyme, the extent of removalof α-D-galactopyranosyl units from the linear chain of mannose units canbe controlled. Additionally or alternatively, a modification of guar maybe obtained by etherification of guar with propyleneoxide orethyleneoxide resulting in a hydroxypropyl guar or hydroxyethyl guar.

In one preferred embodiment of the present invention, the guarderivative is an anionic guar derivative such as a carboxymethyl guar(CMG) and/or carboxymethyl hydroxypropyl guar (CMHPG) and/orcarboxymethyl hydroxyethyl guar (CMHEG). For example, carboxymethyl guaris obtained by reacting a guar with monochloroacetic acid in thepresence of caustic soda.

In another preferred embodiment of the present invention, the guarderivative is a cationic guar derivative obtained by reacting guar withderivatives of quaternary ammonium salts.

The cationic guar derivative and/or anionic guar derivative has a degreeof substitution of the hydroxyl groups of at least 0.01, preferably ofat least 0.05 and may be as high as 2. A suitable degree of substitutionof the hydroxyl groups may be from 0.1 to 1.

The molecular weight of the guar ranges from 1 000 to 1 000 000 Da andis generally about 220 000 Da. The molecular weight of the guar can beadjusted by the treatment with hydrogen peroxide (H₂O₂).

Suitable cationic guar derivatives are available from a wide variety ofcommercial sources. Useful cationic guar derivatives include the guarderivatives available from Polygal AG, Märstetten, Switzerland asPolygal CA-310 D.

Suitable natural guars are available from a wide variety of commercialsources. Useful natural guars include the guar available from SigmaAldrich, Buchs, Switzerland as G4129.

In one preferred embodiment of the present invention, the at least onepolysaccharide is soluble in water.

The term “soluble” in the meaning of the present invention refers tosystems in which no discrete solid particles are observed in thesolvent, i.e. the at least one polysaccharide forms a hydrocolloidalsolution, wherein the hydrocolloid particles of the at least onepolysaccharide are dispersed in the solvent.

The binder can be provided in form of a hydrocolloidal solution or a drymaterial. In one preferred embodiment, the binder is provided in form ofa hydrocolloidal solution.

If the binder is provided in form of a hydrocolloidal solution, thesolution can be in form of an aqueous hydrocolloidal solution, i.e. thepolymeric binder is provided in water. Alternatively, the hydrocolloidalsolution can be in form of an organic suspension, i.e. the polymericbinder is provided in an organic solvent selected from the groupcomprising methanol, ethanol, acetone and mixtures thereof.

For example, the binder is provided in form of an aqueous hydrocolloidalsolution.

In one preferred embodiment of the present invention, the binder is inform of a hydrocolloidal solution having a binder concentration from0.05 wt.-% to 10 wt.-%, preferably from 0.1 wt.-% to 5 wt.-%, morepreferably from 0.1 wt.-% to 2 wt.-% and most preferably from 0.1 wt.-%to 1 wt.-%, based on the total weight of the solution.

Step c): Mixing the Binder with the Aqueous Pigment Material Suspension

According to step c) of the process of the present invention, thepolymeric binder of step b) is mixed with the aqueous pigment materialsuspension of step a).

In one preferred embodiment of the present invention, the binder isadded to the aqueous pigment material suspension in an amount from 0.1wt.-% and 10 wt.-%, preferably from 0.05 wt.-% to 5.0 wt.-%, morepreferably from 0.1 wt.-% to 2 wt.-% and most preferably from 0.25 wt.-%to 1 wt.-%, based on the total weight of the pigment materialsuspension.

The amount of binder in the suspension can be adjusted by methods knownto the skilled person. To adjust the amount of binder in the suspension,the suspension may be partially or fully dewatered by a filtration,centrifugation or thermal separation process. For example, thesuspension may be partially or fully dewatered by a filtration processsuch as nanofiltration or a thermal separation process such as anevaporation process. Alternatively, water may be added to the suspensionuntil the desired amount of binder is obtained.

Additionally or alternatively, the solids content in step c) is adjustedsuch that it is at least 1 wt.-%, preferably from 1 wt.-% to 80 wt.-%,more preferably from 5 wt.-% to 60 wt.-%, even more preferably from 10wt.-% to 50 wt.-% and most preferably from 15 wt.-% to 45 wt.-%, basedon the total weight of the pigment material suspension.

The solids content of the suspension can be adjusted by methods known tothe skilled person. To adjust the solids content of an aqueous pigmentmaterial comprising suspension, the suspension may be partially or fullydewatered by a filtration, centrifugation or thermal separation process.For example, the suspension may be partially or fully dewatered by afiltration process such as nanofiltration or a thermal separationprocess such as an evaporation process. Alternatively, water may beadded to the particulate material of the aqueous pigment materialsuspension (e.g. resulting from filtration) until the desired solidscontent is obtained. Additionally or alternatively, a self-bindingpigment particle suspension having an appropriate lower content of solidparticles may be added to the particulate material of the aqueouspigment material suspension until the desired solids content isobtained.

In the process of the present invention, the binder can be mixed withthe aqueous pigment material suspension by any conventional mixing meansknown to the skilled person.

In one preferred embodiment of the present invention, the aqueouspigment material suspension obtained in step c) has a pH from 6 to 12,preferably from 6.5 to 10 and more preferably from 7 to 9.

The aqueous pigment material suspension can be mixed with the binder inany appropriate form, e.g. in the form of a hydrocolloidal solution or adry material.

Preferably, the binder is in form of a hydrocolloidal solution. In onepreferred embodiment, the binder is in form of an aqueous hydrocolloidalsolution having a binder concentration from 0.05 wt.-% to 10 wt.-%,preferably from 0.1 wt.-% to 5 wt.-%, more preferably from 0.1 wt.-% to2 wt.-% and most preferably from 0.1 wt.-% to 1 wt.-%, based on thetotal weight of the solution.

Step d): Grinding the Aqueous Pigment Material Suspension

According to step d) of the process of the present invention, theaqueous pigment material suspension of step c) is ground.

The grinding process may be undertaken by all the techniques andgrinders well known to the man skilled in the art for wet grinding. Thegrinding step may be carried out with any conventional grinding device,for example, under conditions such that refinement predominantly resultsfrom impacts with a secondary body, i.e. in one or more of: a ball mill,a rod mill, a vibrating mill, a centrifugal impact mill, a vertical beadmill, an attrition mill, or other such equipment known to the skilledperson. The grinding step d) may be carried out in batch orcontinuously, preferably continuously.

In one preferred embodiment of the present invention, the aqueoussuspension to be ground has a pH from 6 to 12, preferably from 6.5 to 10and more preferably from 7 to 9.

Additionally or alternatively, the aqueous suspension obtained aftergrinding has a pH from 6 to 12, preferably from 6.5 to 10 and morepreferably from 7 to 9.

In one preferred embodiment of the present invention, the grinding stepd) is carried out at a temperature from 10° C. to 110° C., preferablyfrom 20° C. to 60° C. and most preferably from 20° C. to 45° C.

In one preferred embodiment of the present invention, grinding step d)is carried out during and/or after step c).

For example, grinding step d) is carried out after step c).

In one preferred embodiment of the present invention, grinding step d)is carried out until the fraction of self-binding pigment particleshaving a particle size of less than 1 μm is greater than 5 wt.-%,preferably greater than 20 wt.-%, more preferably greater than 40 wt.-%,more preferably greater than 50 wt.-%, and most preferably greater than60 wt.-%, based on the total weight of the pigment particles, asmeasured with a Sedigraph 5120.

Additionally or alternatively, the self-binding pigment particlesobtained in step d) of the process of the present invention may have aweight median particle diameter d₅₀, measured according to thesedimentation method, in the range of from 0.05 μm to 3 μm, preferablyfrom 0.1 μm to 2 μm and most preferably from 0.4 μm to 1 μm, for examplefrom 0.6 μm to 0.8 μm. Additionally or alternatively, the self-bindingpigment particles obtained in step d) may have a d₉₈ of less than 10 μmpreferably of less than 5, more preferably of less than 3 and mostpreferably of less than 2 μm.

In one preferred embodiment of the present invention, the self-bindingpigment particles obtained in step d) exhibit a BET specific surfacearea of from 1 m²/g to 201 m²/g, more preferably 3 m²/g to 25 m²/g, mostpreferably 5 m²/g to 15 m²/g and even more preferably 6 m²/g to 12 m²/g,measured using nitrogen and the BET method according to ISO 9277.

In one preferred embodiment of the present invention, the solids contentof the obtained suspension in step d) is at least 1 wt.-%, preferablyfrom 1 wt.-% to 80 wt.-%, more preferably from 5 wt.-% to 60 wt.-%, evenmore preferably from 10 wt.-% to 50 wt.-% and most preferably from 15wt.-% to 45 wt.-%, based on the total weight of the pigment materialsuspension.

In one preferred embodiment of the present invention, the process of theinvention may lead directly to a high solids suspension of self-bindingpigment particles, i.e. the process of the present invention does notrequire an additional concentration step.

If a high solids suspension of self-binding pigment particles isobtained, the solids content of the obtained suspension is at least 45wt.-% and preferably from 45 wt.-% to 80 wt.-%, based on the totalweight of the pigment material suspension. For example, the solidscontent of the obtained suspension is from 50 wt.-% to 80 wt.-%,preferably from 60 wt.-% to 79 wt.-% and more preferably from 65 wt.-%to 78 wt.-%, based on the total weight of the pigment materialsuspension.

In one preferred embodiment of the present invention, the processfurther comprises step e) of concentrating the obtained pigment materialsuspension.

In one preferred embodiment of the present invention, concentration stepe) is carried out before or after step d).

For example, concentration step e) is carried out before step d).Alternatively, concentration step e) is carried out after step d).

If step e) is implemented in the process of the present invention, thesolids content in the obtained suspension is adjusted such that it is atleast 45 wt.-%, preferably from 45 wt.-% to 80 wt.-%, more preferablyfrom 50 wt.-% to 80 wt.-%, even more preferably, from 60 wt.-% to 79wt.-% and most preferably from 65 wt.-% to 78 wt.-%, based on the totalweight of the pigment material suspension.

The solids content of the obtained suspension can be adjusted byconcentrating methods known to the skilled person. The concentrating ofthe corresponding pigment material suspension may be achieved by meansof a thermal process, for example in an evaporator, or by means of amechanical process, for example in a filter press such asnanofiltration, and/or centrifuge.

In one preferred embodiment of the present invention, the processcomprises step e) of concentrating the obtained pigment materialsuspension such that the solids content in the obtained suspension is atleast 65 wt.-%, more preferably at least 80 wt.-% and most preferably atleast 90 wt.-%, based on the total weight of the pigment materialsuspension.

In one preferred embodiment of the present invention, the processcomprises step e) of concentrating the obtained pigment materialsuspension such that a dry product is obtained.

The term “dry product” is understood to refer to pigment particleshaving a total surface moisture content of less than 0.5 wt.-%,preferably less than 0.2 wt.-% and more preferably less than 0.1 wt.-%,based on the total weight of the pigment particles.

If the inventive process further comprises step e) of concentrating theobtained pigment material suspension such that a dry product or asuspension having a solids content of at least 65 wt.-%, more preferablyat least 80 wt.-% and most preferably at least 90 wt.-%, based on thetotal weight of the pigment material suspension, is obtained, the dryproduct or the suspension may be rediluted. If the dry product or thesuspension is rediluted, the solids content in the obtained suspensionis adjusted such that it is at least 1 wt.-%, preferably from 1 wt.-% to80 wt.-%, more preferably from 5 wt.-% to 60 wt.-%, even more preferablyfrom 10 wt.-% to 50 wt.-% and most preferably from 15 wt.-% to 45 wt.-%,based on the total weight of the pigment material suspension.

In one preferred embodiment of the present invention, a dispersing agentis added before or during or after process step c) and/or step d).

In one preferred embodiment of the present invention, the inventiveprocess does not involve the use or addition of a dispersing agentduring grinding.

In view of the very good results of the process for preparingself-binding pigment particle suspensions as defined above, a furtheraspect of the present invention refers to a self-binding pigmentparticle suspension which is obtainable by the process according to thepresent invention.

Such suspension contains a high solids content of self-binding mineralpigment particles, and preferably is free of stabilizing and/ordispersing agents. The inventive self-binding pigment particlesuspension preferably has a low total organic content and/or a lowcontent of free binder in the water phase of the suspension. The totalorganic content and/or content of free binder in the water phase can bedetermined after drying at 120° C. by measuring the loss on ignition(LOI) values at 570° C.

According to another aspect of the present invention, a paper productcomprising self-binding pigment particles is provided, characterized inthat the pigment particles are at least partially coated with at leastone polysaccharide comprising galactose and/or mannose units.

It is preferred that the paper product comprising self-binding pigmentparticles, has a tensile index of at least 10 Nm/g, preferably at least15 Nm/g, more preferably at least 20 Nm/g and most preferably at least22 Nm/g at a filler loading of 20 wt.-%.

The improved tensile index of the products obtained from theself-binding pigment particle suspension of the present inventionindicates a very good adhesion of the binder to the surface of thepigment particles and allows, thus, for the use of the inventiveself-binding pigment particles in several applications, e.g., paper,paint and plastic applications. Another application is the coating oftree leaves and/or plant leaves to reduce sun light and UV exposure ofthe leave surface. Also the good cohesion properties (binding effectbetween particles) provide beneficial properties in such applications.

According to a further aspect of the present invention, the self-bindingpigment particle suspension obtainable by the inventive process is usedas filler material, e.g. in paper, plastics, paint, concrete and/oragriculture applications. According to an exemplary embodiment of thepresent invention, the self-binding pigment particle suspensionobtainable by the inventive process is used in paper, e.g., in wet endprocess of a paper machine, preferably in cigarette paper and/or coatingapplications, or preferably as support for rotogravure and/or offsetand/or digital printing.

It is to be understood that the advantageous embodiments described abovewith respect to the inventive method for making self-binding pigmentparticles also can be used for preparing or defining the inventivesuspension, paper product and its use. In other words, the preferredembodiments described above and any combinations of these embodimentscan also be applied to the inventive suspension, paper product and itsuse.

The scope and interest of the invention will be better understood basedon the following examples which are intended to illustrate certainembodiments of the invention and are non-limitative.

EXAMPLES

Methods and Materials

In the following, materials and measurement methods implemented in theexamples are described.

BET Specific Surface Area of a Material

The BET specific surface area was measured via the BET method accordingto ISO 9277 using nitrogen, following conditioning of the sample byheating at 250° C. for a period of 30 minutes. Prior to suchmeasurements, the sample was filtered, rinsed and dried at 110° C. in anoven for at least 12 hours.

Particle Size Distribution (Mass % Particles with a Diameter <X) andWeight Median Diameter (d₅₀) of a Particulate Material

Weight median grain diameter and grain diameter mass distribution of aparticulate material were determined via the sedimentation method, i.e.an analysis of sedimentation behavior in a gravitational field. Themeasurement was made with a Sedigraph™ 5120.

The method and the instrument are known to the skilled person and arecommonly used to determine grain sizes of fillers and pigments. Themeasurement was carried out in an aqueous solution of 0.1 wt.-% Na₄P₂O₇.The samples were dispersed using a high speed stirrer and ultrasonic.

pH of an Aqueous Suspension

The pH of the aqueous suspension was measured using a standard pH-meterat approximately 22° C.

Solids Content of an Aqueous Suspension

The suspension solids content (also known as “dry weight”) wasdetermined using a Moisture Analyser HR73 from the companyMettler-Toledo, Switzerland, with the following settings: temperature of120° C., automatic switch off 3, standard drying, 5 to 20 g ofsuspension.

Handsheet Study

The handsheet study and the consequent testing of the mechanicalstrength properties of the paper is a measure for the binding ability ofthe self-binding pigment to other surfaces like cellulosic fibres.

Eucalyptus pulp (Jarilyptus) refined to 30° SR was used for this study.60 g (dry) pulp blend were diluted in 10 dm³ tap water, and then thefiller was added. The suspension was stirred for 30 minutes.Subsequently 0.06% (based on dry weight) of a polyacrylamide (Polymin1530, commercially available from BASF, Ludwigshafen, Germany) was addedas a retention aid and sheets of 78 g/m² were formed using theRapid-Köthen hand sheet former. Each sheet was dried using theRapid-Köthen drier. The filler content in the handsheets was determinedby burning a quarter of a dry handsheet in a muffle furnace heated to570° C. After the burning was completed, the residue was transferred ina desiccator and allowed to cool down. When room temperature wasreached, the weight of the residue was measured and the mass was relatedto the initially measured weight of the dry quarter hand sheet. Thefiller content in the examples was 20-30%.

The mechanical strength properties of the handsheets were characterizedby the tensile index and internal bond according to ISO 1924-2 andSCAN-P80:98/TAPPI T541, respectively, after drying of the handsheets.

Tablet Crushing Test

This test is a measure for the self-binding power of a pigment. It is ameasure for the force needed to crush tablets that were formed from theself-binding pigment slurries.

To demonstrate the suitability for the self-binding character of thepigmentary particles thus obtained, tablets were formulated using amembrane filtration process. In this regard, an apparatus of thehigh-pressure filter press type was used, manufactured from a hollowsteel tube. The said tube is closed at the top by a lid and contains thefiltration membrane at the bottom.

Tablets were formed by applying a constant pressure (15 bar) to 80 ml ofthe aqueous pigment material suspension measured for 2 to 48 hours suchthat water is released by filtration through a fine 0.025 μm filtermembrane resulting in a compacted tablet. This method produces tabletsof about 4 cm diameter with a thickness of 1.5 to 2.0 cm. The obtainedtablets were dried in an oven at 60° C. for 48 hours.

The device and method used are described in detail in the documententitled “Modified calcium carbonate coatings with rapid absorption andextensive liquid uptake capacity” (Colloids and Surfaces A, 236 (1-3),2003, pp. 91-102).

Subsequently, the tablets were ground into disc-shaped samples of2.0-2.1 cm diameter with a thickness of 0.6-0.7 cm for the strength testanalysis by using a disk mill (Jean Wirtz, Phoenix 4000). This procedureis described in the document entitled “Fluid transport into porouscoating structures: some novel findings” (Tappi Journal, 83 (5), 2000,pp. 77-78). These smaller tablet discs were crushed under pressure totest their strength property by using the penetration apparatusZwick/Roell Alround Z020 from the company Zwick GmbH & Co. KG, Ulm,Germany. The piston is brought down into contact with the sample at adeformation speed of 3 mm per minute, the test stops at 95% deformationor 20 kN. At the first local maximum in the measurement a crack in thesample occurred. The values given herein are the average of threemeasurements of independently prepared tablets and the error bars arethe standard deviation of these three measurements.

Polyelectrolyte Titration (PET)

The polyelectrolyte content in the aqueous suspension is determinedusing a Memotitrator Mettler DL 55 equipped with a Phototrode DP 660commercialised by Mettler-Toledo, Switzerland. The measurements of thepoylelectrolyte content was carried out by weighing a sample of thecalcium carbonate suspension into a titration vessel and diluting saidsample with deionized water up to a volume of approximately 40 ml.Subsequently, 10 ml of 0.01 M cationicpoly(N,N-dimethyl-3,5-dimethylene-piperidinium chloride) (PDDPC;obtained from ACROS Organics, Belgium) are slowly added under stirringinto the titration vessel within 5 min. and than the content of thevessel is stirred for another 20 min. Afterwards the suspension isfiltered trough a 0.2 μm mix-ester membrane filter (Ø 47 mm) and washedwith 5 ml of deionized water. The thus obtained filtrate is diluted with5 ml of phosphate buffer pH 7 (Riedel-de Haën, Germany) and than 0.01 Mof a potassium polyvinylsulfate (KPVS; obtained from SERVAFeinbiochemica, Heidelberg) solution is added slowly to the filtrate totitrate the excess of cationic reagent. The endpoint of titration isdetected by a Phototrode DP660, which is adjusted to 1200 to 1400 mV indeionized water, prior to such measurement. The charge calculation iscarried out according to the following evaluation:

$Q_{atro} = {\frac{\left( {\left( {V_{PDDPC}*t_{PDA}} \right) - V_{KPVS}} \right)*\left( {- 1000} \right)}{E_{P}*{Fk}}\mspace{14mu}\left\lbrack {{µ{Val}}\text{/}g} \right\rbrack}$$w_{atro} = {- {\frac{Q_{atro}}{K_{DM}*100}\mspace{14mu}\lbrack\%\rbrack}}$

Calculation of the optimal sample weight:

$E_{P} = \frac{60}{w_{DM}*K_{DM}*{Fk}}$

Calculation of adapted sample weight for 4 ml consumption:

$E_{4\mspace{14mu}{ml}} = \frac{E_{1}*6}{\left( {10 - V_{{KPVS},1}} \right)}$

Abbreviations

E_(P)=sample weight [g]

w_(DM)=Dispersing agent content in [%]

K_(DM)=Dispersing agent constant [μVal/0.1 mg dispersing agent]

Fk=Solids content [%]

V_(PDDPC)=Volume PDDPC [ml]

V_(KPVS)=Volume KPVS [ml]

t_(PDDPC)=Titer PDDPC

E_(DM)=Dispersing agent weight [mg]

Q=Charge [μVal/g]

w_(atro)=Dispersing agent content atro [%]

E₁=Sample weight of experiment to be optimised [g]

V_(KPVS,1)=experimental consumption KPVS [ml] of experiment to beoptimised

Loss on Ignition (LOI) Method

For the measurement of the loss on ignition, samples of the self-bindingpigment material suspensions were dried in a microwave at approximately200 W for about 75 min such that the samples have maximum moisture ofabout 0.5 wt.-%, based on the total weight of the particulate material.Subsequently, the dried samples were de-agglomerated by using a RETSCHultra-centrifugal mill (type ZM) with 200 μm screen and rotor having 24teeth. 3 to 4 g of the obtained sample was weighed into a porcelaincrucible and heated in a muffle oven at about 570° C. until constantmass. After cooling in a desiccator, the porcelain crucible was weighedwith the obtained residue. The values given herein are the average oftwo measurements of independently prepared samples.

The loss on ignition is an absolute measurement displayed in percent andcalculated according to the following formula:

$\frac{100*\left( {m_{1} - m_{2}} \right)}{m_{1}}$withm₁: mass of initial weight [g]m₂: mass after heating to about 570° C. in a muffle oven [g]

Example 1 (Inventive Example)

The particulate material used for the preparation of the slurry was amarble of Norwegian origin.

The pigment slurry had a solids content of about 20 wt.-%, based on thetotal weight of the suspension. The particulate material has a weightmedian particle diameter d₅₀ value of 0.8 μm, a d₉₀ of less than 2 μmand a d₆₀ of less than 1 μm (all measured according to the sedimentationmethod). Furthermore, the particulate material of the slurry had aspecific surface area of 7 m²/g (measured using nitrogen and the BETmethod).

A powder of guar in an amount of 0.4% by weight (commercialised by SigmaAldrich under G4129), based on the total weight of the suspension, wasblended before grinding into the suspension of the particulate materialand stirred with a dissolver stirrer for 30 minutes.

The low solid suspension at ˜20 wt.-% was run through a DynomillMultilab filled with 460 cm³ Verac grinding beads (0.6-1.0 mm) for 90minutes. The grinding chamber had a total volume of 600 cm³. The millspeed was set to 2 500 rpm and the flow was set to 500 cm³/min. Grindingwas carried out at room temperature.

No significant increase in temperature was observed.

The product obtained was analysed by Sedigraph®, solids content, PET, pHand LOI. Table 1 summarizes the measured details of the final product.

TABLE 1 Inventive Example 1 <2 μm/% 97.7 <1 μm/% 83.0 D₅₀/μm 0.56 solidscontent/wt.-% 20.2 PET/μEq/g −14.8 pH 6.28 LOI/% 2.6

In addition thereto, the effect of the self-binding pigment particlesuspensions on the tensile index for handsheets prepared from thesuspension obtained in Example 1 is outlined in FIG. 1.

Furthermore, the effect of the self-binding pigment particle suspensionson the internal bond (in z-Direction) for handsheets prepared from thesuspension obtained in Example 1 is outlined in FIG. 2.

For comparative reasons, also the tensile index and the effect on theinternal bond (in z-Direction) for handsheets prepared from a suspensioncomprising a commercially available product have been measured. Thepigment particles used therefore are commercially available asHydrocarb® HO-ME from Omya International AG, Oftringen, Switzerland. Theproduct is in the form of a suspension of a natural CaCO₃ and has asolids content of 66 wt.-%, based on the total weight of the suspension.The particulate material in the suspension, measured on a Sedigraph5120, has a weight median particle diameter d₅₀ value of 0.8 μm, a d₉₀of less than 2 μm and a d₆₀ of less than 1 μm. Furthermore, theparticulate material of the Hydrocarb® HO-ME has a specific surface areaof 7 m²/g (measured using nitrogen and the BET method).

From FIGS. 1 and 2, it can be concluded that handsheets prepared from asuspension made in accordance with the inventive process achieve atensile index of about 22 Nm/g and internal bond (in z-Direction) of atleast 475 kPa. In contrast thereto, the measured tensile index of thehandsheets prepared from the suspension comprising the commerciallyavailable pigment particles was 20 Nm/g, while the internal bond (inz-Direction) of below 400 kPa. Thus, it has to be assumed that thesuspensions of self-binding pigments particles obtained by the inventiveprocess impart positive effects on the mechanical strength properties ofend products prepared from said suspensions.

Example 2 (Comparative Example)

The particulate material used for the preparation of the slurry was amarble of Norwegian origin.

The pigment slurry had a solids content of about 20 wt.-%, based on thetotal weight of the suspension. The particulate material has a weightmedian particle diameter d₅₀ value of 0.8 μm, a d₉₀ of less than 2 μmand a d₆₀ of less than 1 μm (all measured according to the sedimentationmethod). Furthermore, the particulate material of the slurry had aspecific surface area of 7 m²/g (measured using nitrogen and the BETmethod).

The low solid suspension at ˜20 wt.-% was run through a DynomillMultilab filled with 460 cm³ Verac grinding beads (0.6-1.0 mm) for 90minutes. The grinding chamber had a total volume of 600 cm³. The millspeed was set to 2 500 rpm and the flow was set to 500 cm³/min.

No significant increase in temperature was observed.

A powder of guar in an amount of 2% by weight (commercialised by SigmaAldrich under G4129), based on the total weight of the suspension, wasblended after grinding into the suspension and stirred for a shortperiod of time. PET measurements of the guar showed an anionic charge of≤−150 μEq/g.

The final product was analysed by Sedigraph®, solids content, PET, pHand LOI. Table 2 summarizes the measured details before the addition ofguar and after the addition of guar.

TABLE 2 Comparative Example 2 Before addition of guar After addition ofguar <2 μm/% 96.7 97.0 <1 μm/% 77.9 68.8 D₅₀/μm 0.61 0.77 solidscontent/wt.-% — 19.4 PET/μEq/g — −16.8 pH — 6.41 LOI/% — 2.7

From the measured details, it can be concluded that the addition of guarafter grinding the aqueous pigment material suspension results in anincreased weight median particle diameter d₅₀ value of the particulatematerial. Furthermore, it can be concluded that the amount ofparticulate material in the suspension having a weight median particlediameter value of less than 1 μm is decreased. Thus, it has to beassumed that the comparative example results in an undesiredagglomeration of particulate material in the suspensions.

Example 3 (Inventive Example)

The particulate material used for the preparation of the slurry was amarble of Norwegian origin.

The pigment slurry had a solids content of about 20 wt.-%, based on thetotal weight of the suspension. The particulate material has a weightmedian particle diameter d₅₀ value of 0.8 μm, a d₉₀ of less than 2 μmand a d₆₀ of less than 1 μm (all measured according to the sedimentationmethod). Furthermore, the particulate material of the slurry had aspecific surface area of 7 m²/g (measured using nitrogen and the BETmethod).

A powder of guar in an amount of 0.4% by weight (commercialised by SigmaAldrich under G4129), based on the total weight of the suspension, wasblended before grinding into the suspension of the particulate materialand stirred with a dissolver stirrer for 60 minutes.

The low solid suspension at ˜20 wt.-% was run through a DynomillMultilab filled with 460 cm³ Verac grinding beads (0.6-1.0 mm) for 90minutes. The grinding chamber had a total volume of 600 cm³. The millspeed was set to 2 500 rpm and the flow was set to 500 cm³/min. Grindingwas carried out at room temperature.

No significant increase in temperature was observed.

Tablets were prepared and measured in the tablet crushing test withrespect to the maximum force, F_(max), required to make the first crackinto a tablet. In particular, tablets were prepared from the suspensionobtained in this Example and tablets prepared from suspensionscomprising the commercially available products Covercarb® 75-ME having aweight median particle diameter d₅₀ value of 0.6 μm, Hydrocarb® 90-MEhaving a weight median particle diameter d₅₀ value of 0.7 μm orOmyacarb® 1-AV having a weight median particle diameter d₅₀ value of 1.7μm (all available from Omya AG, Oftringen, Switzerland) but withoutusing a binder.

The effect of the self-binding pigment particle suspensions on themaximum force, F_(max), required to make the first crack into a tabletas measured in the tablet crushing test is outlined in FIG. 3.

From FIG. 3 it can be concluded that tablets prepared from a suspensionmade in accordance with the inventive process require a maximum force ofabout 1 400 N to make the first crack compared to a required maximumforce of less than 350 N for tablets prepared without binder. Thus, ithas to be assumed that the suspensions of self-binding pigmentsparticles obtained by the inventive process impart positive effects onthe mechanical strength properties of end products prepared from saidsuspensions.

The invention claimed is:
 1. Paper, plastic, paint, concrete or anagriculture product comprising self-binding pigment particles preparedby the process comprising the following steps: a) providing an aqueouspigment material suspension, wherein the pigment of the pigment materialsuspension comprises calcium carbonate; b) providing a polymeric binder,wherein the binder consists of at least one polysaccharide comprisinggalactose and/or mannose units; c) mixing 0.1 wt.-% to 10 wt.-% of thebinder of step b), based on the total weight of the aqueous pigmentmaterial suspension, with the aqueous pigment material suspension ofstep a), to obtain a mixture of the binder and the aqueous pigmentmaterial suspension; and d) grinding the mixture of the binder and theaqueous pigment material suspension obtained in step c) to obtain asuspension of self-binding pigment particles, wherein the weight mediandiameter (d₅₀) of the self-binding pigment particles is less than theweight median diameter (d₅₀) of the pigment from step a).
 2. The paper,plastic, paint, concrete or an agriculture product according to claim 1,wherein the pigment material of the pigment material suspension of stepa) comprises calcium carbonate and one or more of-dolomite, magnesium,clay, talc, kaolin, aluminium hydroxide, mica, titanium dioxide,synthetic fibers or natural fibers.
 3. The paper, plastic, paint,concrete or an agriculture product according to claim 1, wherein thepigment material of the pigment material suspension of step a) is aground natural calcium carbonate, a precipitated calcium carbonate, amodified calcium carbonate, or any mixture thereof.
 4. The paper,plastic, paint, concrete or an agriculture product according to claim 1,wherein the pigment material of the pigment material suspension of stepa) is a ground natural calcium carbonate.
 5. The paper, plastic, paint,concrete or an agriculture product according to claim 1, wherein thebinder of step b) is at least one polysaccharide comprising galactoseand mannose units.
 6. The paper, plastic, paint, concrete or anagriculture product according to claim 1, wherein the binder of step b)is at least one polysaccharide comprising a linear chain of 1,4-linkedβ-D-mannopyranosyl units or a linear chain of 1,4-linkedβ-D-mannopyranosyl units with 1,6-linked α-D-galactopyranosyl units. 7.The paper, plastic, paint, concrete or an agriculture product accordingto claim 1, wherein the binder of step b) is at least one polysaccharidehaving a ratio of mannose units to galactose units from 6:1 to 1:1. 8.The paper, plastic, paint, concrete or an agriculture product accordingto claim 1, wherein the binder of step b) is at least one polysaccharidehaving a ratio of mannose units to galactose units from 5:1 to 1:1. 9.The paper, plastic, paint, concrete or an agriculture product accordingto claim 1, wherein the binder of step b) is at least one polysaccharidehaving a ratio of mannose units to galactose units from 4:1 to 1:1. 10.The paper, plastic, paint, concrete or an agriculture product accordingto claim 1, wherein the binder of step b) is at least one polysaccharidehaving a ratio of mannose units to galactose units from 3:1 to 1:1. 11.The paper, plastic, paint, concrete or an agriculture product accordingto claim 1, wherein the binder of step b) is in a form of ahydrocolloidal solution or a dry material.
 12. The paper, plastic,paint, concrete or an agriculture product according to claim 1, whereinthe binder of step b) is in a form of a hydrocolloidal solution having abinder concentration from 0.05 wt.-% to 10 wt.-%, based on the totalweight of the solution.
 13. The paper, plastic, paint, concrete or anagriculture product according to claim 1, wherein the binder of step b)is in a form of a hydrocolloidal solution having a binder concentrationfrom 0.1 wt.-% to 5 wt.-%, based on the total weight of the solution.14. The paper, plastic, paint, concrete or an agriculture productaccording to claim 1, wherein in step c) 0.05 wt.-% to 5.0 wt.-% of thebinder of step b), based on the total weight of the aqueous pigmentmaterial suspension, is mixed with the aqueous pigment materialsuspension of step a).
 15. The paper, plastic, paint, concrete or anagriculture product according to claim 1, wherein in step c) 0.1 wt.-%to 2 wt.-% of the binder of step b), based on the total weight of theaqueous pigment material suspension, is mixed with the aqueous pigmentmaterial suspension of step a).
 16. The paper, plastic, paint, concreteor an agriculture product according to claim 1, wherein in step c), thepigment material suspension has a solids content of 5 wt.-% to 80 wt.-%,based on the total weight of the pigment material suspension.
 17. Thepaper, plastic, paint, concrete or an agriculture product according toclaim 16, wherein in step c), the pigment material suspension has asolids content of 10 wt.-% to 60 wt.-%, based on the total weight of thepigment material suspension.
 18. The paper, plastic, paint, concrete oran agriculture product according to claim 1, wherein grinding step d) iscarried out at a temperature from 10° C. to 110° C.
 19. The paper,plastic, paint, concrete or an agriculture product according to claim 1,wherein grinding step d) is carried out until the fraction ofself-binding pigment particles having a particle size of less than 1 μmis greater than 20 wt.-%, based on the total weight of the pigmentparticles.
 20. The paper, plastic, paint, concrete or an agricultureproduct according to claim 1, wherein grinding step d) is carried outuntil the fraction of self-binding pigment particles having a particlesize of less than 1 μm is greater than 50 wt.-%, based on the totalweight of the pigment particles.
 21. The paper, plastic, paint, concreteor an agriculture product according to claim 1, wherein the suspensionof self-binding pigment particles obtained in step d) is concentratedsuch that the solids content in the suspension is from 45 wt.-% to 80wt.-%, based on the total weight of the pigment material suspension. 22.The paper, plastic, paint, concrete or an agriculture product accordingto claim 1, wherein before or during or after step c) and/or step d) adispersing agent is added.
 23. The paper, plastic, paint, concrete or anagriculture product according to claim 1, which is paper.
 24. The paper,plastic, paint, concrete or an agriculture product according to claim 1,which is plastic.
 25. The paper, plastic, paint, concrete or anagriculture product according to claim 1, which is paint.
 26. The paper,plastic, paint, concrete or an agriculture product according to claim 1,which is concrete.
 27. The paper, plastic, paint, concrete or anagriculture product according to claim 1, which is an agriculturalproduct.